Polymeric thickeners for aqueous compositions

ABSTRACT

Latexes are thickened by compounds of the formula ##STR1## wherein R 1  is an aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical having a valence of from 2 to 8; each of B 1  -B 8  is independently an ester, amide, amine, ether, sulfide, disulfide, thiocarbamate, urea, thiourea, urethane, sulfate, phosphate, carbonyl, methylene, thioamide, carbonate, or imide linkage; each of X 1  -X 8  is independently --A 1  --R 2  --A 2  -- or --A 1  -- wherein each of A 1  and A 2  is independently an ester, amide, amine, ether, sulfide, disulfide, urethane, thiocarbamate, urea, thiourea, sulfate, phosphate, carbonyl, methylene, thioamide, carbonate, or imide linkage and R 2  is a divalent aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical with the proviso that only one of B 1  -B 8  is urethane and that when one of B 1  -B 8  is urethane, one of A 1  and A 2  is not urethane; each of d, g, j, m, p, s, v, y is independently 0 or 1, each of c, f, i, l, o, r, u, x is independently any integer or non-integer from 0 to about 200; each of J, K, L, M, N, P, Q, S is 0 or 1; each of e, h, k, n, q, t, w, z is independently any integer or non-integer from 0 to about 200; each of R 3  -R 10  is independently an aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical having from 1 to about 50 carbon atoms; each of AG and AO is independently an ethyleneoxy, 1,2-propyleneoxy, 1,2-butyleneoxy unit or combinations thereof.

CROSS REFERENCES TO RELATED APPLICATIONS

This application is a division of application Ser. No. 08/727,983, now U.S. Pat. No. 5,728,895, filed Oct. 9, 1996 which is a continuation of application Ser. No. 08/350,496, now abandoned, filed Dec. 6, 1994 which is a continuation of application Ser. No. 08/074,695, now abandoned, filed Jun. 8, 1993 which is a continuation of application Ser. No. 07/787,905, now abandoned, filed Nov. 7, 1991 which is a continuation-in-part of application Ser. No. 07/611,206, now abandoned, filed Nov. 8, 1990.

FIELD OF THE INVENTION

This invention relates to polymeric compounds which are useful as thickeners for aqueous compositions especially emulsion polymer latexes.

DESCRIPTION OF THE RELATED ART

Many aqueous systems require thickeners in order to be useful for various types of applications. Such aqueous-based systems as cosmetics, protective coatings for paper and metal, printing inks, and latex paints all require the incorporation of thickeners in order to have the proper rheological characteristics for their particular uses. Many substances useful as thickeners are known in the art. These include natural polymers such as casein and alginates, and synthetic materials such as cellulose derivatives, acrylic polymers, and polyurethane polymers. Polyurethanes have found particular application as latex paint thickeners. British patent 1,069,735 teaches a process for making water soluble or water swellable surface active products. One aspect of G.B. 1,069,735 teaches that a polymer of the formula R--Y--A--Y--R wherein R is a hydrocarbon radical having more than 8 carbon atoms, Y is the group --NHCOO--, and A is a polyethylene glycol ether by reaction of a polyethylene glycol ether having a molecular weight of at least 1,000 with a monofunctional isocyanate of the formula RNCO wherein R is a hydrocarbon radical having more than 8 carbon atoms. Another aspect of G.B. 1,069,735 teaches that a polymer of the formula R--Y--(A--T)_(n) --A--Y--R wherein R is a hydrocarbon radical having more than 8 carbon atoms, Y is the group --NHCOO--, A is a polyethylene glycol ether, T is a diisocyanate residue, and n is a whole number ≦10 can be made by reaction of a polyethylene glycol ether having a molecular weight of at least 1,000 with a monofunctional isocyanate of the formula RNCO wherein R is a hydrocarbon radical having more than 8 carbon atoms. A third aspect taught by G.B. 1,069,735 is that a polymer of the formula R--X--(A--T)_(n) --A--X--R wherein R is a hydrocarbon radical having more than 8 carbon atoms; x is the group --NHCOO--, --SCONH--, --NHCONH--,)N--CONH--, or --CONH--; A is a polyethylene glycol ether, T is the diisocyanate residue, and n is a whole number ≦10 by reaction of a polyethylene glycol ether having a molecular weight of at least 1,000 and a diisocyanate so that an excess of isocyanate groups is present over those needed to react with the hydroxyl groups of the polyethylene glycol and a monofunctional alcohol, mercaptan, phenol, or carboxylic acid or a primary or secondary amine, said monofunctional compound has a hydrocarbon radical having more than 8 carbon atoms; in which process the total amount of hydrocarbon radical which contains more than 8 carbon atoms does not amount to >6% by weight of the reaction product. Japanese Kokai Patent 48-97783 teaches that compounds of the formula ##STR2## wherein Z is a polyether polyol residue derived from a compound containing active hydrogen atoms and alkylene oxide in which the polyether contains 20%-90% by weight oxyethylene groups; m is a number ranging from 2 to 8 and which signifies the number of hydroxyl groups per polyether polyol molecule; A is the residue of a divalent organic group such as a tolylene diisocyanate residue; Y is a residue of a compound containing active hydrogen atoms such as an ethoxylated C₁₄ aliphatic alcohol; and n is a number equal to at least 3 can be used as thickeners in aqueous media such as in latex paints. U.S. Pat. No. 4,079,028 teaches a latex paint composition containing an emulsion polymer and from 0.1 to about 10% by weight based on emulsion polymer solids of a thickener selected from polymers of Groups A, B, and C. Polymers of group A are linear polymers of the formula A--B_(p) --E_(q) --(B--E)_(m) --B_(r) --E_(t) --A wherein each of p, q, r, and t independently, is zero or 1; at least one of q and r is 1, and t is zero when r is zero; provided that, when q is 1, then: (a) each of p, r, and t is zero; or (b) p is zero and each of r and t is 1; or (c) t is zero and each of r and p is 1; and when q is zero, then r is 1 and each of p and t is zero; A is a hydrophobic organic radical containing at least one carbon atom; B is a divalent hydrophobic group of the structure ##STR3## where G is the residue of an organic di- or triisocyanate; E is a divalent, hydrophilic, nonionic polyether group of molecular weight of at least about 1,500 and m is at least 1. Polymers of group B are designated are star-shaped products of the formula [H--E--OCH₂ ]_(S) L [Q_(v) --(D_(u) --E--A)_(w) R_(z) ]_(m) where L is X, Y or --O--, Q is --CH₂ C.tbd., D is --CH₂ O--, m is 2-4, s is zero to 2 the sum of m and s is the valence of L, w is 1-3, and each of u and z independently is zero or 1; and where X is a hydrocarbon radical containing at least 1 carbon atom, preferably 1-4 carbon atoms; and Y is a trivalent radical selected from --OCONH(CH₂)₆ N[CONH(CH₂)₆ NHCO--O]₂ --, CH₃ C[CH₂ --O--OCNHC₇ H₆ NHCO]₃ --, and CH₃ CH₂ C[CH₂ --O--OCNHC₇ H₆ NHCO]₃ -- provided that: (a) when L is X, then u and w are each 1, v and z are each zero, the sum of m and s is 4, and m is at least 2; (b) when L is Y, then u, v and s are each zero, m is 3, w is 2-3, and z is zero or 1; (c) when L is --O--, then v and u are each 1, m is 2, w is 1-3, and each of s and z is zero. Polymers of group c are complex mixtures of linear, branched, and sub-branched products which form networks or hydrophobes and hydrophobic segments interspersed with hydrophilic segments. The essential elements of these polymers are a polyfunctional compound containing at least 3 hydroxyl or isocyanate groups, a difunctional compound reactive with the polyfunctional compound, and a monofunctional reactant such as a monohydroxy or monoamino compound. U.S. Pat. No. 4,155,892 teaches a composition consisting essentially of water and an amount of a thickener polymer selected from the polymers disclosed in U.S. Pat. No. 4,079,028 above to thicken the water. U.S. Pat. No. 4,499,233 teaches a water dispersable modified polyurethane which is the product of the reaction of: (a) a polyisocyanate; (b) a polyether polyol; (c) a modifying agent which is a multifunctional compound such as α, ω-amino alkanes and aromatic diamines such as 1,4-diaminobenzene; and (d) a capping agent such as a monoisocyanate. U.S. Pat. No. 4,499,233 also teaches a thickened aqueous composition comprised of water and from about 0.005 to about 10.00% by weight of a water dispersable modified polyurethane as disclosed above.

U.S. Pat. No. 4,426,485 teaches thickeners for aqueous systems which are water-soluble polymers having a molecular weight of at least 10,000 and which are comprised of hydrophobic segments each containing at least one monovalent hydrophobic group covalently bonded to the polymer. At least one of the hydrophobic segments has at least two hydrophobes thereby forming a bunch of hydrophobes within the hydrophobic segment. The hydrophobes within a bunched hydrophobic segment are in close association when they are separated by no more than about 50 covalently bonded, sequentially connected atoms. One example of such a polymer is made by reacting a polyurethane pre-polymer comprised of PEG 8000 and toluene diisocyanate with toluene diisocyanate and the diol formed by reaction of epichlorohydrin and a 10 mole ethylene oxide adduct of nonyl phenol.

A non-urethane thickener is disclosed in U.S. Pat. No. 3,770,684 which teaches latex compositions containing from about 0.1% to about 3.0% of a compound of the general formula R--X--(water soluble polyether)--X--R' wherein R and R' are water insoluble hydrocarbon residues; X is a connecting linkage selected from the group consisting of an ether linkage, an ester linkage, an amide linkage, an imino linkage, a urethane linkage, an sulfide linkage, or a siloxane linkage. U.S. Pat. No. 3,770,684 also teaches that the preferred water soluble polyether is a polyethylene oxide polymer having a molecular weight of from 3,000 to 35,000 or an ethylene oxide-propylene oxide copolymer having a molecular weight of from 3,000 to 35,000.

The compounds according to the present invention are water soluble or highly dispersable in water and do not normally require the incorporation of volatile organic cosolvents in commercial formulations. In addition, the compounds according to the invention are more efficient thickeners for aqueous compositions than thickeners of the prior art.

SUMMARY OF THE INVENTION

Compounds which are useful as thickeners for aqueous compositions particularly latex paints have the formula ##STR4## wherein R¹ is an aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical having a valence of from 2 to 8; each of B₁ -B₈ is independently an ester, amide, amine, ether, sulfide, disulfide, thiocarbamate, urea, thiourea, urethane, sulfate, phosphate, carbonyl, methylene, thioamide, carbonate, or imide linkage; each of X¹ -X⁸ is independently --A₁ --R² --A₂ -- or --A₁ -- wherein each of A₁ and A₂ is independently an ester, amide, amine, ether, sulfide, disulfide, urethane, thiocarbamate, urea, thiourea, sulfate, phosphate, carbonyl, methylene, thioamide, carbonate, or imide linkage and R² is a divalent aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical with the proviso that only one of B₁ -B₈ is urethane and that when one of B₁ -B₈ is urethane, one of A₁ and A₂ is not urethane; each of d, g, j, m, p, s, v, y is independently 0 or 1, each of c, f, i, l, o, r, u, x is independently any integer or non-integer from 0 to about 200; each of J, K, L, M, N, P, Q, S is 0 or 1; each of e, h, k, n, q, t, w, z is independently any integer or non-integer from 0 to about 20; each of R³ -R¹⁰ is independently an aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical having from 1 to about 50 carbon atoms; each of AG and AO is independently an ethyleneoxy, 1,2-propyleneoxy, 1,2-butyleneoxy unit or combinations thereof.

Thickened aqueous compositions are comprised of water and a thickening-effective amount of one or more of a compound of the formula I and a latex composition comprising an emulsion polymer and from about 0.1 to about 20 percent by weight based on emulsion polymer solids of a compound of the formula I.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Other than in the operating examples, or where otherwise indicated, all numbers expressing quantities of ingredients or reaction conditions used herein are to be understood as modified in all instances by the term "about".

In regard to Figure I, the abbreviations (AO) and (AG) stand for the ethyleneoxy group --CH₂ CH₂ O--, the 1,2-propyleneoxy group --CH₂ CH(CH₃)O--, or the 1,2-butyleneoxy group --CH(CH₂ CH₃)CH₂ O-- or combinations thereof. Each of the subscripts c, f, i, l, o, r, u, x is independently any integer or non-integer from 0 to about 200 and each of the subscripts e, h, k, n, q, t, w, z is independently any integer or non-integer from 0 to about 20. One of ordinary skill in the art will appreciate that the non-integer values for the subscripts reflect the fact that they represent the average degree of alkoxylation. In the case of subscripts e, h, k, n, q, t, w, z the upper limit value is about 20. Compounds having degrees of alkoxylation, AG, greater than 20 do not give minimum thickening when incorporated into a composition comprised of water and an emulsion polymer or when incorporated into a latex paint formulation. The abbreviations NP and DNP stand for nonylphenoxy and dinonylphenoxy respectively. For purposes of this invention, it is understood that aliphatic includes cycloaliphatic and heterocycloaliphatic wherein the heteroatoms are nitrogen, oxygen, sulfur, and phosphorus. In regard to the values of A₁ and A₂, the ester, amide, amine, ether, sulfide, disulfide, and urethane linkages are respectively ##STR5## The thiocarbamate, thiourea, urea, sulfate, and phosphate linkages are respectively ##STR6## The carbonyl, methylene, thioamide, imide, and carbonate linkages are respectively ##STR7##

Each of R³ -R¹⁰ is independently an aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical having from 1 to about 50 carbon atoms. R¹ is aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical having a valence of from 2 to 8. Such aliphatic radicals include any di- to octavalent: (a) straight chain and branched alkyl radicals having from 2 to about 50 carbon atoms; (b) cycloalkyl radicals having from 4 to about 20 carbon atoms; (c) straight chain and branched alkenyl radicals having from 2 to about 40 carbon atoms; (d) cycloalkenyl radicals having from 5 to about 20 carbon atoms; (e) straight chain and branched alkynyl radicals having from 2 to about 30 carbon atoms; cycloalkynyl radicals having from 6 to about 20 carbon atoms. Aliphatic radicals also include those, above-mentioned aliphatic radicals which contain one or more heteroatoms substituted for one or more hydrogen atoms. The heteroatoms include the halogens, nitrogen, sulfur, oxygen, and phosphorus or groups of heteroatoms such as nitro, sulfonic acid, C₁₋₁₀ alkyl sulfonate ester, sulfoxide, sulfone, phosphoryl, trihalomethyl, and the like. Examples of unsubstituted alkyl radicals include but are not limited to: ##STR8## An aromatic radical is any benzenoid or non-benzenoid aromatic radical having a valence of 2 to 8. A non-benzenoid aromatic radical includes carbocyclic and heterocyclic aromatic radicals. For purposes of this invention, a substituted aromatic radical is any benzenoid or non-benzenoid aromatic radical having a valence of from 2 to 6 wherein one or more hydrogen atoms is replaced by an atom or a group of atoms other than hydrogen including the halogens, nitrogen, sulfur, oxygen, and phosphorus or groups of heteroatoms such as nitro, sulfonic acid, C₁₋₁₀ alkyl sulfonate ester, sulfoxide, sulfone, phosphoryl, trihalomethyl, and the like. Such an aromatic radical includes those radicals which contain aliphatic moieties and/or hetero atoms as exemplified in the following structures II, III and IV: ##STR9## wherein in formula IV, R¹² has the same value as R¹ and γ is any integer or non-integer from 1 to about 400. For example, in formula IV, when R¹² is a bis-phenol A residue, then R¹ would have the following structure ##STR10## wherein δ is any integer or non-integer from 1 to about 400.

Each of B₁ -B₈ is an ester, amide, amine, ether, sulfide, disulfide, thiocarbamate, urea, urethane, thiourea, sulfate, phosphate, carbonyl, methylene, thioamide, carbonate, or imide linkage as disclosed above for A₁ and A₂. While only one of B₁ -B₈ can be a urethane linkage each one of B₁ -B₈ can be identical when one of B₁ -B₈ is not a urethane linkage. For example, each or all of B₁ -B₈ can be an ether linkage or an ester linkage. The values of A₁ and A₂ are limited by the value of B₁ -B₈ such that when one of B₁ -B₈ is urethane, only one of A₁ and A₂ is also urethane.

The compounds according to the invention are polymeric materials which can be made by any process within the purview of those having ordinary skill in the art. One preferred method is a step-wise process, the first step of which comprises forming an adduct of the formula R¹ --B--(AO)_(c) --OH wherein R¹, and c are defined as above. The symbol B in the formula for the adduct is a generic representation of B₁ -B₈ and can have any value which B₁ -B₈ can have. The adduct will form the center or core of a compound of the formula I because it contains R₁ and the linking groups B₁₋₈. The adduct can be made by reacting a compound of the formula R¹ --(B'Z)₁₋₈ wherein R¹ is defined as above and each B'Z is a precursor of an ester, amide, amine, ether, sulfide, disulfide, thiocarbamate, urea, urethane, thiourea, sulfate, phosphate, carbonyl, methylene, thioamide, carbonate, or imide linkage which when reacted with a polyether or an alkylene oxide will result in the formation of the respective linkage with a polyether so that each terminal atom of the functional groups of R¹ --(B'Z)₁₋₈ is bonded to a terminal atom of a polyether chain. For example, if the adduct is a diester formed by reaction of adipic acid and PEG 6000, then R¹ is --(CH₂)₄ --and each of B₁ and B₂ is an ester linkage. In this instance, Z of R¹ --(B'Z)₁₋₈ could be hydrogen. This adduct can be made by direct or trans esterification of adipic acid with PEG 6000 using a dicarboxylic acid/polyether molar ratio which would ensure that the major product is the OH-terminated diester and not polyester. Another way of making the same adduct would be by direct ethoxylation of adipic acid with about 136 moles of ethylene oxide for each carboxyl group. In another example, if the adduct is a diamine residue, then R¹ --(B'Z)₁₋₈ wherein R¹ is --CH₂ CH₂ --, B is an amine linkage and Z is hydrogen could be made by direct propoxylation of ethylene diamine with propylene oxide. The adduct can be formed from any aliphatic or aromatic carboxylic acid, ester, amine, hydrophobic alcohol, isocyanate, sulfide, disulfide, ketone, urea, or imide having the formula R¹ --(B'Z)₁₋₈ wherein R¹ and B'Z are defined as above such that when it is reacted with either a ethyleneoxide, 1,2-propyleneoxide, 1,2-butyleneoxide or a combination thereof or a polyethyleneoxide, poly-1,2-propyleneoxide, or poly-1,2-butyleneoxide or copolymers thereof, the adduct will have the formula R¹ --(B)₁₋₈ --(AO).sub.β --OH wherein R¹, and B are defined as above and β has a value of from 1.5 to about 200.

The use of a hydrophobic alcohol to form the core of the adduct described above results in the formation of a hydrophobic ether residue as R¹. A hydrophobic ether residue has the formula HE(O).sub.α -- wherein HE is a hydrophobic group and α is an integer having a value of from 2 to 8. A hydrophobic group is any group which would contribute to the water insolubility of the ether residue. Unsubstituted aliphatic groups having at least 4 carbon atoms, aromatic groups having 6 or more carbon atoms and groups which contain both aliphatic and aromatic moieties are hydrophobic. Examples of polyfunctional hydrophobic ether residues include but are not limited to the trimethylolpropoxy group, diphenoxy group, a diether residue of a diol produced by hydrogenation of the dimethyl ester of a dimer acid, and the bis-(2-hydroxypropyl) ether of bisphenol A.

Each of AO and AG of formula I represent an ethyleneoxy (EO), 1,2-propyleneoxy (PO), 1,2-butyleneoxy (BO) unit or combinations thereof such that each of AO and AG is a water soluble, or water dispersable polyether group. The water solubility or water dispersability of a polyether group is a function of its molecular structure and/or its molecular weight. For example, an EO homopolymer having a molecular weight of about 20,000 daltons or less is water soluble while a water soluble PO homopolymer has a molecular weight of less than about 700 daltons. The structure of an EO-PO copolymer must be such that it contains from about 50 wt % to about 75 wt % of ethyloxy groups to be water soluble. The structure-property relationships of EO and PO polyethers is described in the Encyclopedia of Polymer Science and Engineering, Second Edition, Volume 6, pages 225-273, John Wiley, 1986, while those of poly BO are described in Volume 6, page 300.

The second step of the process is reaction of the adduct formed in the first step with a monofunctional capping reagent which has a general formula R³⁻¹⁰ --(AG)_(e) --XY wherein R³⁻¹⁰, AG, and e are defined as above; X is --A₁ --R² --Z wherein A₁ and R² are defined as above and Y is a functional group capable of reacting with the terminal OH group of the adduct R¹ --(B)₁₋₈ --(AO)_(c) --OH to form an ester, amide, amine, ether, sulfide, disulfide, urethane, thiocarbamate, urea, thiourea, sulfate, phosphate, carbonyl, methylene, thioamide, carbonate, or imide linkage between R² and --(AO).sub.β --. For example, Y is a group capable of reacting with the terminal --OH group of the polyether when Y is a carboxyl group, isocyanate group, thiocyanate group, acyl halide group, an epoxy group, or a chlorosulfonyl group. When Y is a halomethyl group for example, it is capable of reacting with a terminal metal alkoxide derivative of the polyether to yield a methylene linkage between the polyether and the capping reagent. The capping reagent can be made from any alkoxylated aliphatic-alcohol or phenol derivative as disclosed herein and any aliphatic or aromatic compound which has two functionalities capable of reaction with the --OH group of an aliphatic alcohol or a phenol including a dicarboxylic acid, an isocyanate, a dihaloalkane, or an epihalohydrin. Examples of capping reagents include but are not limited to the mono adipic acid ester of an ethoxylated nonyl phenol and the glycidyl ether of an ethoxylated nonyl phenol. The method of synthesis of the capping reagent depends upon the nature of the capping reagent.

Another preferred process for making the thickeners according to the invention is a step-wise process the first step of which comprises forming an adduct between an aliphatic, substituted aliphatic, aromatic, or substituted aromatic compound having 2 to 8 functional groups capable of reacting with an alkylene oxide or a polyalkylene oxide so that each terminal atom of the functional groups is bonded to a terminal atom of the polyoxyalkylene chain. Put in terms of formula I, a terminal atom of a polyoxyalkylene chain is covalently bonded to R¹ through the functional groups designated as B₁ -B₈. The method of making the adduct is a function of the nature of the linking group. For example, if each OH group of glycerol is ethoxylated with ethylene oxide, then in terms of formula I, R¹ is a 1,2,3-propanetriyl group of the formula ##STR11## and each of B₁ -B₃ is an ether linkage. In another example, if trimellitic acid is esterified with a polyethylene glycol or ethoxylated with ethylene oxide, then R¹ is a 1,2,4-trisubstituted phenyl group of the formula ##STR12## and each of B₁ -B₃ is an ester linkage. The second step involves the capping of the adduct described by any one of a number of compounds which will result in a compound of formula I. For example, an ethoxylated glycerol adduct could be capped with the half NP--(EO)₂ --OH ester of succinic acid to form a compound of formula I in which R¹ is 1,2,3-propanetriyl; M,N,P,Q,S are each zero; J, K and L are each equal to one; each of B₁, B₂ and B₃ is an ether linkage; R³, R⁴, and R⁵ are each nonylphenyl, (AG) and (AO) are each ethyleneoxy, c and f range from about 50 to about 150, d, e, g, h i, j, and k are each zero; and X¹ and X² are each a succinate ester moiety such that each of A₁ and A₂ is an ester linkage and R² is an ethylene radical. Other methods of making the thickeners according to the invention are set forth in Examples 1-14.

An example of a compound wherein R¹ is an aromatic radical having a valence of four and which contains an aliphatic moiety and a hetero atom can be made starting with 3,3',4,4'-benzophenone tetracarboxylic anhydride which is available from Chriskev company, Inc. The anhydride can be reacted with a polyalkylene oxide such as polyethylene glycol to yield an adduct which can then be used in one of the preferred processes as disclosed herein. An example of a compound wherein R¹ is an aliphatic radical having a valence of six and which contains a hetero atom can be made starting with dipentaerythritol or pentaerythritol dimer. The dimer can be alkoxylated with an alkylene oxide to yield an adduct which can then be used in one of the preferred processes as disclosed herein. An example of a compound wherein R¹ is an aliphatic radical having a valence of eight and which contains a hetero atom can be made starting with tripentaerythritol or pentaerythritol trimer. The trimer can be alkoxylated with an alkylene oxide to yield an adduct which can then be used in one of the preferred processes as disclosed herein. An example of a compound wherein R¹ is an aliphatic radical having a valence of four and which contains a hetero atom can be made starting with a dianhydride ketone as taught by U.S. Pat. No. 3,600,406, the entire contents of which are incorporated herein by reference. The anhydride can be reacted with a polyalkylene oxide such as polyethylene glycol to yield an adduct which can then be used in one of the preferred processes as disclosed herein.

The ester, amide, amine, ether, sulfide, disulfide, thiocarbamate, urea, urethane, thiourea, sulfate, phosphate, carbonyl, methylene, thioamide, carbonate, or imide linkages can be incorporated into the compounds according to the invention either as A₁ and A₂ or B₁ -B₈ linkages by any method known to those skilled in the art. Examples of such methods include but are not limited to the following reactions. The references listed for the reactions refer to Szmant, Organic Chemistry, Prentice Hall, Inc., 1957; Whitmore, Organic Chemistry, D. Van Nostrand Co., Inc., 1951; and Wagner & Zook, Synthetic Organic Chemistry, J. Wiley & Sons, Inc., 1953.

In a case wherein R₁ is m-phenylene, B₁ and B₂ can be a sulfate linkage by reacting equimolar quantities of resorcinol, NP(EO)₅₀ --OH and sulfuric acid. (See Szmant pp 245-6; Whitmore p 158). In a case wherein R₁ is m-xylyl, B₁ and B₂ can be a sulfide linkage by reacting equimolar quantities of 1,3-dichloromethylbenzene (available as α,α'-dichloro-m-xylene from Adrich Chemical Co., Milwaukee, Wis.), NP(EO)₅₀ --SH in the presence of sodium hydroxide. (See Szmant pp 519-520; Whitmore p 146). NP(EO)₅₀ --SH can be made from NP(EO)₅₀ --OH and thionyl chloride followed by reaction with a sulfide salt. In a case wherein R₁ is m-xylyl, B₁ and B₂ can be a disulfide linkage by reacting equimolar quantities of 1,3-bis(thiomethyl)benzene (Berichte, 42, 4346 (1909)) and NP(EO)₅₀ --SH in the presence of hydrogen peroxide. (See Szmant pp 519-520; Whitmore p 146). In a case wherein R₁ is m-phenylene, B₁ and B2 can be a phosphate linkage by reacting resorcinol and phosphorus pentoxide followed by partial transesterification with NP(EO)₅₀ --OH (See Szmant pp 240, 245, 247). In a case wherein R₁ is 1,2,3-propanetriyl B₁ and B₂ can be a thiocarbamate linkage by reaction of glycerol with an isothiocyanate (See Szmant p 470). In a case wherein R₁ is m-phenylene, B₁ and B₂ can be a thiourea linkage by reacting m-diaminobenzene and an isothiocyanate (See Whitmore p 446). In a case wherein R₁ is m-phenylene, B₁ and B₂ can be a carbonate linkage by reacting equimolar quantities of resorcinol, NP(EO)₅₀ --OH and phosgene (See Whitmore p 480). In a case wherein R₁ is m-phenylene, B₁ and B₂ can be an imide linkage by reacting iso-phthaloyl dichloride, urea, and the acid chloride corresponding to NP(EO)₅₀ --OH by oxidation of NP(EO)₅₀ --OH followed by reaction with thionyl chloride (See Wagner & Zook, p576). In a case wherein R₁ is p-phenylene, B₁ and B₂ can be a urea linkage by reacting 1,4-phenylene diisocyanate (available from Aldrich Chemical Co., Milwaukee, Wis.) and NP(EO)₅₀ --NH₂ which can be made by aminolysis of the corresponding halide (See Szmant pp 436-7).

One group of preferred compounds includes those wherein R¹ is a divalent aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical; L,M,N,P,Q,S are each zero; J and K are each equal to one; each of B₁ and B₂ is an ester linkage; R³ and R⁴ are each nonylphenyl, (AG) and (AO) are each ethyleneoxy, c and f are each equal to from about 90 to about 185, e and h are each about 1.5; each of X¹ and X² is --A₁ --R² --A₂ -- wherein each of A₁ and A₂ is an ether linkage and R² is a divalent aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical. Another group of preferred compounds includes those wherein R¹ is a divalent aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical; L,M,N,P,Q,S are each zero; J and K are each equal to one; each of B₁ and B₂ is an ether linkage; R³ and R⁴ are each nonylphenyl, (AG) and (AO) are each ethyleneoxy, c and f are each equal to from about 90 to about 185, e and h are each about 1.5; each of X¹ and X² is --A₁ --R² --A₂ -- wherein each of A₁ and A₂ is an ether linkage and R² is a divalent aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical. Another group of preferred compounds are those wherein R¹ is bis-(2-hydroxypropyl) ether of bisphenol A which has the formula ##STR13## and L,M,N,P,Q,S are each zero; J and K are each equal to one; each of B₁ and B₂ is an ether linkage; R³ and R⁴ are each nonylphenyl, (AG) and (AO) are each ethyleneoxy, c and f are each equal to from about 90 to about 185, e and h are each about 1.5; each of X¹ and X² is --A₁ --R² --A₂ -- wherein each of A₁ and A₂ is an ether linkage and R² is a divalent aliphatic, substituted aliphatic, aromatic, or substituted aromatic radical. Yet another group of preferred compounds are those wherein R¹ is meta-xylyl; L,M,N,P,Q,S are each zero; J and K are each equal to one; each of B₁ and B₂ is an ether linkage; R³ and R⁴ are each nonylphenyl, (AG) and (AO) are each ethyleneoxy, e and h range from about 90 to about 185, c, d, f and g are each zero. Still another group of preferred compounds are those wherein R¹ is 1-chloroethylidene; L,M,N,P,Q,S are each zero; J and K are each equal to one; each of B₁ and B₂ is an ether linkage; R³ and R⁴ are each nonylphenyl, (AG) and (AO) are each ethyleneoxy, e and h range from about 50 to about 150, c, d, f and g are each zero. A further group of preferred compounds are those wherein R¹ is 1,2,3-propanetriyl; M,N,P,Q,S are each zero; J, K and L are each equal to one; each of B₁, B₂ and B₃ is an ether linkage; R³ and R⁴ are each nonylphenyl, R⁵ is benzyl, substituted benzyl, or C₅₋₁₀ alkyl; (AG) and (AO) are each ethyleneoxy, e and h range from about 50 to about 150, c, d, f, g i, j, and k are each zero. Another group of preferred compounds are those in which R¹ is a tetravalent group of the formula ##STR14## wherein R¹¹ is an aliphatic, substituted aliphatic, aromatic, heteroaromatic, substituted aromatic, or substituted heteroaromatic group; N,P,Q,S are each zero; J, K, L, and M are each equal to one; each of B₁, B₂, B₃, and B₄ is an ether linkage; each of R³, R⁴ R⁵, and R⁶ is nonylphenyl; (AG) and (AO) are each ethyleneoxy, e, h, k, and n each range from about 90 to about 185, c, d, f, g, i, j, 1, and m are each zero. A particularly preferred thickener for high gloss, styrene-acrylic latex paint is a composition comprised of a mixture of compounds of the formula V ##STR15## This mixture results from the synthetic method used to prepare a thickener having the above general molecular formula. The method, which is described in Example 5, produces a mixture of compounds that differ in the degree of ethoxylation because two different surfactants, NP--(EO)₁₀₀ --OH and NP--(EO)₁₂₅ --OH, are reacted with the epichlorohydrin. The resulting product contains a mixture of six compounds which differ only in the values of e, h, k, and n wherein: (a) each of e, h, k, and n is equal to 100; (b) each of e, h, k, and n is equal to 125; (c) three of e, h, k, and n is equal to 125 and one of e, h, k, and n is equal to 100; (d) three of e, h, k, and n is equal to 100 and one of e, h, k, and n is equal to 125; (e) any two of e, h, k, and n is equal to 100 and any two of e, h, k, and n is equal to 125; (f) one of e and h is equal to 100 and the other one of e and h is equal to 125, one of e and h is equal to 125 and the other one of e and h is equal to 100. It will be appreciated by those skilled in the art that such a mixture of compounds will result whenever two or more different surf actants are used in a process to make the thickeners according to the invention such as that described in Examples 2, 5, 6, 11, and 12. Another particularly preferred composition for thickening high gloss styrene-acrylic paint is one which contains a mixture of three compounds of formula I wherein for each compound R¹ is meta-xyly; L,M,N,P,Q,S are each zero; J and K are each equal to one; each of B₁ and B₂ is an ether linkage; R³ and R⁴ are each nonylphenyl, (AG) is ethyleneoxy, c, d, f and g are each zero, and: (a) e and h are each equal to about 125; (b) e and h are each equal to about 100; (c) one of e and h is equal to about 125 and the other of e and h is equal to about 100.

A group of particularly preferred thickeners for acrylic-based latex paint are compounds of the formula VI ##STR16## wherein R¹ is ##STR17## Aqueous compositions comprised of thickeners according to the invention are also part of the invention. These compositions are comprised of water and a thickening-effective amount of one or more compounds of formula I. A thickening-effective amount is any amount required to bring the Brookfield viscosity of the aqueous composition to from about 3,000 to about 5,000 cps (spindle #3, @30 r.p.m.). This amount will typically be from about 1 to about 50% by weight of one or both types of compounds according to the invention. An aqueous composition according to the invention is comprised of from about 1 to about 50% by weight of one or more compounds according to the invention, from about 1% to about 30% by weight of a viscosity modifier which is a compound selected from the group consisting of a liquid polyol, a liquid ethoxylated or propoxylated C₁₋₈ alcohol, or a liquid ethoxylated or propoxylated C₁₋₈ carboxylic acid. A liquid polyol is any compound having two or more --OH groups which is a liquid at room temperature examples of which include but are not limited to ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol. A liquid ethoxylated or propoxylated C₁₋₈ alcohol is any aliphatic alcohol ethoxylated or propoxylated to any degree of ethoxylation or propoxylation and which is a liquid. Compounds in which the --OH group of the liquid ethoxylated or propoxylated C₁₋₈ alcohol is etherified with a C₁₋₄ alkyl group are also included in this group. A liquid ethoxylated or propoxylated C₁₋₈ carboxylic acid is any aliphatic carboxylic acid ethoxylated or propoxylated to any degree of ethoxylation or propoxylation and which is a liquid. Preferred viscosity modifiers include butoxy triglycol (triethylene glycol monobutyl ether), butyl carbitol (diethylene glycol monobutyl ether), or 1,2-propylene glycol. Also preferred are combinations of butoxy triglycol, butyl carbitol, and 1,2-propylene glycol which total from about 1% to about 30% by weight of the total composition. An aqueous composition will typically contain about 40% by weight of water, about 40% by weight of a thickener according to the invention and about 20% by weight of one or a combination of butoxy triglycol, butyl carbitol and 1,2-propylene glycol. The preferred composition is comprised of about 40% by weight of water, about 40% by weight of a thickener according to the invention and about 20% by weight of butoxy triglycol.

The thickeners according to the invention also afford commercial thickener products which have important economic and practical advantages over conventional thickener products because they contain significantly greater amounts of thickener per unit weight of product. For example, typical commercial thickeners are aqueous compositions containing from about 20% to about 30% by weight thickener and having a Brookfield viscosity of about 15,000 cps. Thickener products containing thickeners according to the invention can be sold commercially as aqueous-based compositions containing from about 35% to about 40% by weight thickener and having Brookfield viscosities ranging from about 400-20,000 cps. The thickeners according to the invention afford commercial products which are higher in solids and are easier to handle because of their lower viscosities. Some of the thickeners which have the general formula V also exhibit the advantage of being able to be sold commercially as aqueous solutions having no organic cosolvents. Such products enjoy the obvious health and safety benefits concomitant with purely aqueous solvents.

The thickeners according to the invention are very efficient in increasing the high shear and low shear viscosities of latexes or latex paint compositions into which they have been incorporated. Latexes are emulsions or dispersions of water insoluble polymers in water. Latex paint compositions typically contain at least an aqueous emulsion or dispersion of a water insoluble polymer, a pigment, a pigment dispersant, a thickener to control the viscosity and improve the leveling and flow characteristics of the paint, and a preservative which is effective in controlling the growth of microorganisms. Present paint industry standards call for a latex paint having an ICI viscosity of from about 0.8 to about 3.0 poise and a Stormer viscosity of from about 90 to about 110 KU. The ICI viscosity is a high shear viscosity and is measured on the ICI (Research Equipment Limited) Cone and Plate Viscosimeter at a shear rate of 10,000 sec⁻¹. The Stormer viscosity is given in Krebs Units (KU) and is measured according to ASTM D662-81. The latexes which can be thickened with the thickeners according to the invention are those disclosed in U.S. Pat. No. 4,079,028 at column 12 line 64 to column 14, line 7 inclusive the entire contents of which are incorporated herein by reference. The thickening ability of the compounds according to the invention can vary with the type of substance to be thickened. For example, some compounds are very efficient at thickening acrylic latexes and not as efficient at thickening styrene-acrylic latexes while others exhibit the opposite behavior. In addition, the thickening ability of a particular compound may also change when that compound is used in a paint formulation as opposed to a composition comprising only latex and water. Table 1 shows the thickening ability of some of the compounds according to the invention in three different latex-based systems.

                  TABLE 1                                                          ______________________________________                                                           STYRENE-        PAINT                                          ACRYLIC.sup.2  ACRYLIC.sup.3  FORMULATION.sup.4                              SAMPLE.sup.1                                                                          ICI    KU      PHR.sup.5                                                                           ICI  KU    PHR.sup.5                                                                           ICI  KU                             ______________________________________                                         1      4.1    87      2    1.2  101   2    1.4   85                              2 2.0 70 3 0.8  90 2 1.4 100                                                   3 3.0 90 2 0.8 123 2 1.4 102                                                   4 3.4 90 3 1.2 123 2 1.3  92                                                   5 1.9 69 3 0.7  74 3 1.4  85                                                   6 3.9 85 3 1.3 122 2 1.4  95                                                 ______________________________________                                          .sup.1 Thickener #1 is RM 1020 ™, a product of Rohm & Haas, Co.             Thickener #2 is from Example 3                                                 Thickener #3 is from Example 8                                                 Thickener #4 is from Example 10                                                Thickener #5 is from Example 7                                                 Thickener #6 is from Example 2                                                 .sup.2 Refers to the viscosities of a thickener at 6 PHR in Ac64 ™, an      all acrylic latex which is a product of Rohm & Haas, Co.                       .sup.3 Refers to the viscosities of a thickener in HG74 ™, a                styreneacrylic latex which is a product of Rohm & Haas, Co.                    .sup.4 Refers to a paint formulated with HG74 ™.                            .sup.5 Parts of thickener per hundred parts of latex or paint formulation

For most commercial applications, a latex is thickened by adding a sufficient amount of an aqueous composition according to the invention to a latex to bring the ICI viscosity into the 0.8 to 3.0 poise range and the Stormer viscosity into the 95 to 105 KU. Typically this amount will be in the range of from about 0.1% to about 10% of the thickener according to the invention by weight of latex polymer solids and preferably between it and 3% by weight of latex polymer solids. The following examples are meant to illustrate but not limit the invention.

EXAMPLE 1

Preparation of ##STR18##

To a 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head were added 1 part of NP--(EO)₁₀₀ --OH (surfactant) and 2 parts of toluene. The mixture was heated to azeotropically distill off the water with stirring +N₂ sparge. After the water concentration is less than 50 ppm the mixture was cooled to 55° C. Sodium methoxide was added in an amount that OH:NaOMe=1:1 based on the calculated hydroxyl value of surfactant. Heat was applied to distill off formed methanol by distilling off half of the initial weight of toluene from the flask. The reaction mixture was then refluxed for 1 hour. The flask was cooled to 85° C. and one-half mole of meta-dichloromethyl benzene was added per mole sodium alkoxide. The reaction mixture was maintained at 85° C. for about 2 hours. When alkalinity by titration approached zero, the remaining toluene was vacuum stripped and butoxytriglycol (BTG) and water were added to give a clear yellow BTG/H₂ O/product ratio of 1:2:2 by weight.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          3.5   88                                              ______________________________________                                    

EXAMPLE 2

This example illustrates the preparation of a composition which contains a mixture of three compounds. The mixture was prepared according to the procedure outlined in Example 1 and contains compounds of the formula I wherein for each compound R¹ is meta-xyly; L,M,N,P,Q,S are each zero; J and K are each equal to one; each of B₁ and B₂ is an ether linkage; R³ and R⁴ are each nonylphenyl, (AG) is ethyleneoxy, c, d, f and q are each zero, and: (a) e and h are each equal to about 100; (b) e and h are each equal to about 125; (c) one of e and h is equal to about 125 and the other of e and h is equal to about 100. The procedure of Example 1 was followed except that the surfactant was composed of NP--(EO)₁₀₀ --OH and NP--(EO)₁₂₅ --OH in a molar ratio of 1.4 moles of NP--(EO)₁₀₀ --OH and 1.0 moles of NP--(EO)₁₂₅ --OH.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          3.9   86                                              ______________________________________                                    

EXAMPLE 3

Preparation of ##STR19##

To a first 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head were added 1 part of NP--(EO)₁₅₀ --OH (surfactant) and 2 parts of toluene. To a second 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head were added 1 part of NP--(EO)₅₀ --OH (surfactant) and 2 parts of toluene. Both flasks were heated to azeotropically distill off the water with stirring +N₂ sparge. After the water concentration in each flask was less than 50 ppm the mixture was cooled to 55° C. Sodium methoxide was added to each flask in an amount that OH:NaOMe =1:1 based on the calculated hydroxyl value of surfactant. Heat was applied to distill off formed methanol by distilling off half of the initial weight of toluene from the flask. In the first flask, the reaction mixture was then refluxed for 1 hour. The flask was cooled to 60° C. after which 1.1 moles of epichlorohydrin were added per mole sodium alkoxide. The reaction mixture was then maintained at 70° C. for about 2 hours. When alkalinity by titration approached zero, the excess epichlorohydrin was vacuum stripped. A 4.0 gram aliquot of the reaction mixture +4 grams of tetraethylammonium bromide were dissolved in 50 ml of glacial acetic acid and the resulting solution titrated with a 0.1036 N HClO₄ in glacial acetic acid solution to a methyl violet end point for the amount of epoxide (epoxy titration). The difference in the total alkalinity minus the HClO₄ titration equals the amount of epoxide. The contents of the first and second flasks were mixed in a third flask such that the epoxy/alkoxide molar ratio was equal to 1:1 and the contents heated to 75-85° C. for 2 hours. When the epoxy titration value equaled zero, 1-chlorooctane was added such that the mole ratio of Cl:ONa was 1:1. The reaction mixture was then refluxed until the alkalinity titration value was zero. Butoxytriglycol (BTG) and water were added to give a clear yellow BTG/H₂ O/product ratio of 1:2:2 by weight.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          2.0   70                                              ______________________________________                                    

EXAMPLE 4

Preparation of ##STR20##

This compound was made according to the procedure of Example 3 in except that the 1-chlorooctane was replaced by benzyl chloride on a mole-for-mole basis.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          1.3   65                                              ______________________________________                                    

EXAMPLE 5

This example illustrates the preparation of a composition which contains a mixture of three compounds of the formula I wherein for each compound R¹ is 1,2,3-propanetriyl; M,N,P,Q,S are each zero; J, K, and L are each equal to one; each of B₁, B₂, and B₃ is an ether linkage; R³ and R⁴ are each nonylphenyl, R⁵ is benzyl; (AG) is ethyleneoxy, c, d, f, g, i, j, and k are each zero, and: (a) e and h are each equal to about 125; (b) e and h are each equal to about 100; (c) one of e and h is equal to about 125 and the other of e and h is equal to about 100. The mixture was prepared by adding to a 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head 1 mole each of NP--(EO)₁₀₀ --OH and NP--(EO)₁₂₅ --OH (surfactant) and 100 grams of toluene. The mixture was heated to azeotropically distill off the water with stirring +N₂ sparge. After the water concentration is less than 50 ppm the mixture was cooled to 60° C. Sodium methoxide was added in an amount that OH:NaOMe=1:1 based on the calculated hydroxyl value of surfactant. The reaction mixture was heated to 125° C. to distill off toluene/methanol which took about 2 hrs. The contents of the flask were cooled to 60° C. and sufficient epichlorohydrin was added so that the epichlorohydrin:alkoxide ratio was 0.55:1.0. The reaction mixture was maintained at 60° C. with stirring and nitrogen sparge for about 4 hours. When alkalinity by titration reached one-half its original value and the epoxide value reached zero, sufficient benzyl chloride was added so that the Cl:ONa ratio was equal to 1:1. The reaction mixture was then refluxed at 125° C. until the alkalinity titration approached zero. Which took about 5 hrs. The remaining toluene was vacuum stripped and butoxytriglycol (BTG) and water were added to give a clear yellow BTG/H₂ O/product ratio of 1:2:2 by weight.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          2.2   75                                              ______________________________________                                    

EXAMPLE 6

This example illustrates the preparation of a composition which contains a mixture of three compounds and is an exact duplicate of Example 5 in every respect except that NP--(EO)₁₀₀ --OH and NP--(EO)₁₂₅ --OH were replaced by NP--(EO)₁₀₀ --OH and NP--(EO)₁₅₀ --OH on an equimolar basis.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          2.4   80                                              ______________________________________                                    

EXAMPLE 7

Preparation of ##STR21##

The procedure of Example 5 was repeated except that all of the surfactant was NP--(EO)₁₅₀ --OH and the benzyl chloride was replaced by meta-dichloromethyl benzene on a 1 mole of benzyl chloride to 0.5 mole meta-dichloromethyl benzene basis.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Latex                                    Thickener  (6 PHR)                                                           Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          1.9   69                                              ______________________________________                                    

EXAMPLE 8

Preparation of ##STR22##

The procedure of Example 5 was repeated except that all of the surfactant was NP--(EO)₁₀₀ --OH and the benzyl chloride was replaced by meta-dichloromethyl benzene on a 1 mole of benzyl chloride to 0.5 mole meta-dichloromethyl benzene basis.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          3.0   90                                              ______________________________________                                    

EXAMPLE 10

Preparation of ##STR23##

The compound was made according to the procedure of Example 1 except that NP--(EO)₁₀₀ --OH was replaced by NP--(EO)₁₂₅ --OH on an equimolar basis.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          3.4   90                                              ______________________________________                                    

EXAMPLE 11

This example illustrates the preparation of a composition which contains a mixture of six compounds. The mixture contained compounds of the formula I wherein N,P,Q,S are each zero; J, K, L and M are each equal to one; each of B₁, B₂, B₃ and B₄ is an ether linkage; R³, R⁴, R⁵ and R₆ are each nonylphenoxy, (AG) is ethyleneoxy, c, f, i, l, o, r, u, and x are each zero; and wherein e, h, k, and n are each equal to 100 or 125 or a combination thereof as explained below and R¹ is ##STR24## wherein: (a) each of e, h, k, and n is equal to 100; (b) each of e, h, k, and n is equal to 125; (c) three of e, h, k, and n is equal to 125 and one of e, h, k, and n is equal to 100; (d) three of e, h, k, and n is equal to 100 and one of e, h, k, and n is equal to 125; (e) any two of e, h, k, and n is equal to 100 and any two of e, h, k, and n is equal to 125; (f) one of e and h is equal to 100 and the other one of e and h is equal to 125, one of e and h is equal to 125 and the other one of e and h is equal to 100. This composition was made by the procedure outlined in Example 5 except that all of the surfactant was a mixture of NP--(EO)₁₀₀ --OH and of NP--(EO)₁₂₅ --OH in a molar ratio of 1.4 moles of NP--(EO)₁₀₀ --OH and 1.0 moles of NP--(EO)₁₂₅ --OH and the 1-chlorooctane was replaced by meta-dichloromethyl benzene on a 1 mole of 1-chlorooctane to 0.5 mole meta-dichloromethyl benzene basis.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          3.5   102                                             ______________________________________                                    

EXAMPLE 12

This example illustrates the preparation of a composition which contains a mixture of three compounds. The mixture was prepared according to the procedure outlined in Example 1 and contains compounds of the formula I wherein for each compound R¹ is meta-xylyl; L,M,N,P,Q,S are each zero; J and X are each equal to one; each of B₁ and B₂ is an ether linkage; R³ and R⁴ are each nonylphenyl, (AG) is ethyleneoxy, c, d, f and g are each zero, and: (a) e and h are each equal to about 125; (b) e and h are each equal to about 100; (c) one of e and h is equal to about 150 and the other of e and h is equal to about 125. The procedure of Example 1 was followed except that the surfactant was composed of equimolar amounts of NP--(EO)₁₂₅ --OH and NP--(EO)₁₀₀ --OH.

    ______________________________________                                         Physical Properties                                                                                         35% Solids                                            Styrene-Acrylic                                                              Thickener  Latex (6 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         300-600   39-41          3.5   102                                             ______________________________________                                    

EXAMPLE 13

Preparation of ##STR25##

To a first 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head were added 1 part of DNP--(EO)₆ --OH and 2 parts of toluene. To a second 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head were added 1 part of bis-phenol A ethoxylated with about 180 moles of ethylene oxide and 2 parts of toluene. Both flasks were heated to azeotropically distill of f the water with stirring +N₂ sparge. After the water concentration in each flask was less than 50 ppm the mixture was cooled to 60° C. Sodium methoxide was added to each flask in an amount that OH:NaOMe=1:1 based on the calculated hydroxyl value of surfactant. Heat was applied to distill off formed methanol by distilling off half of the initial weight of toluene from the flask then the contents were refluxed for 1 hour with N₂ sparge. The flask was cooled to 60° C. after which 1.1 moles of epichlorohydrin were added per mole sodium alkoxide. The reaction mixture was then maintained at 70° C. until the alkalinity by titration approached zero. The excess epichlorohydrin was vacuum stripped. A 4.0 gram aliquot of the reaction mixture +4 grams of tetraethylammonium bromide were dissolved in 50 ml of glacial acetic acid and the resulting solution titrated with a 0.1036 N HClO₄ in glacial acetic acid solution to a methyl violet end point for the amount of epoxide (epoxy titration). The difference in the total alkalinity minus the HClO₄ titration equals the amount of epoxide. The contents of the first flask were added to the second flask, which had been cooled to 110° C. in an amount such that the epoxy/alkoxide molar ratio was equal to 1:1. This mixture was held at 110° C. overnight. When the epoxy titration value equaled zero, the remaining toluene was vacuum distilled. Butoxytriglycol (BTG) and water were added to give a clear yellow BTG/H₂ O/product ratio of 1:5:3 by weight.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (3 PHR)                                                     Visc.     Solids         ICI    KU                                             ______________________________________                                         700       30%            0.70   66                                             ______________________________________                                    

EXAMPLE 14

Preparation of ##STR26## wherein R¹ is ##STR27##

To a first 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head were added 1 part of NP--(EO)₁.5 --OH and 2 parts of toluene. To a second 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head were added 1 part of polyethylene glycol (M.W.=8,000) and 2 parts of toluene. Both flasks were heated to azeotropically distill off the water with stirring +N₂ sparge. After the water concentration in each flask was less than 50 ppm the mixture was cooled to 60° C. Sodium methoxide was added to each flask in an amount that OH:NaOMe=1:1 based on the calculated hydroxyl value of surfactant. Heat was applied to distill off formed methanol by distilling off half of the initial weight of toluene from the flask then the contents were refluxed for 1 hour with N₂ sparge. The first flask was cooled to room temperature while maintaining reflux in the second flask. To the first flask one mole of meta-dichloromethyl benzene was added per mole sodium alkoxide and the reaction mixture was then maintained at 60° C. until the alkalinity by titration approached zero. The contents of the second flask were cooled to 60° C. and then the contents of the first flask were added to it so that the dichloromethylbenzene to sodium alkoxide ratio was 1.05:1.00. The temperature as maintained at 60° C. until the alkalinity approached zero. The remaining toluene was vacuum distilled. Butoxytriglycol (BTG) and water were added to give a cloudy-white BTG/H₂ O/product ratio of 1:2:2 by weight.

    ______________________________________                                         Physical Properties                                                                                         35% Solids Acrylic                                  Thickener  Latex (3 PHR)                                                     Visc.     Solids         ICI   KU                                              ______________________________________                                         1900      40%            1.8   124                                             ______________________________________                                    

Comparative Example

Preparation of ##STR28##

This example illustrates the effect of the degree of alkoxylation of the alkyleneoxy group adjacent to R³⁻¹⁰ on the performance of the thickener. When the degree of ethoxylation of the alkyleneoxy group adjacent to R³⁻¹⁰ is equal to or greater than 20, the compound does not thicken a latex.

A capping reagent was prepared by adding to a 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head about 1 part of NP--(EO)₂₀ --OH (surfactant) and 2.5 parts of toluene. The mixture was heated to azeotropically distill off the water with stirring +N₂ sparge. After the water concentration is less than 50 ppm the mixture was cooled to 55° C. Sodium methoxide was added in an amount that OH:NaOMe=1:1 based on the calculated hydroxyl value of surfactant. Heat was applied to distill off 98 grams total of methanol and toluene from the flask. The reaction mixture was then refluxed for 1 hour. The flask was cooled to 90° C. and one mole of meta-dichloromethyl benzene was added per mole sodium alkoxide. The reaction mixture was refluxed until the alkalinity by titration approached zero.

To another 250 ml round bottom flask equipped with a stirrer, nitrogen inlet tube, and a distillation head were added 1 part of bis-phenol A ethoxylated with about 180 moles of ethylene oxide [HO--(EO)₉₀ --BPA--(EO)₉₀ --OH] and one part of toluene. The mixture was heated to azeotropically distill off the water with stirring +N₂ sparge until the hydroxyl number reached 12.9. Sodium methoxide was added in an amount that OH:NaOMe=1:1 based on the calculated hydroxyl value of surfactant. Heat was applied to distill off 47 grams total of methanol and toluene from the flask and the hydroxyl value of the material in the flask reached 12. About 12 grams of the capping reagent were added and the reaction mixture heated until about it alkalinity by weight remained as determined by HCl titration. The remaining toluene was vacuum stripped and butoxytriglycol (BTG) and water were added to give BTG/H₂ O/product ratio of 1:2:2 by weight. This compound did not thicken either an acrylic or styrene-acrylic latex at any commercially useful concentrations. 

What is claimed is:
 1. An aqueous composition comprising water and a thickening-effective amount of a thickener of the formula ##STR29## wherein R¹ is a member selected from the group consisting of straight chain or branched aliphatic groups having from 3 to about 50 carbon atoms, cycloalkyl groups having from 4 to 20 carbon atoms, straight chain or branched unsaturated aliphatic groups having from 3 to about 40 carbon atoms, cycloalkenyl groups having from 5 to about 20 carbon atoms, and aromatic groups having from 6 to about 21 carbon atoms having a valence of 3 or 4; each of c, f, i, and l is independently 0 or any integer from about 50 to about 200 with the proviso that at least two of c, f, i and l cannot be 0; each of J, K, L and M is 0 or 1, provided that at least three of J, K, L and M are 1; each of R³ -R⁶ is independently an aliphatic or aromatic group having from 1 to 50 carbon atoms; and each AO is independently an ethyleneoxy, 1,2-propyleneoxy, 1,2-butyleneoxy group or combinations thereof and when one of J, K, L or M is 0, the valence is filled by hydrogen.
 2. A composition of claim 1 wherein R¹ is 1,2,3-propanetriyl; M is zero; J, K and L are each equal to one; R³ and R⁴ are each nonylphenyl, R⁵ is benzyl, substituted benzyl, or C₅₋₁₀ alkyl; (AO) is ethyleneoxy, and c, f, and i are each zero.
 3. A composition of claim 1 wherein R¹ is ##STR30## wherein J, K, L and M are each equal to one; R³, R⁴, R⁵ and R₆ are each nonylphenyl, and c, f, i, and l, are each zero.
 4. An aqueous composition of claim 1 wherein said thickener is a mixture of compounds wherein for each compound R¹ is 1,2,3-propanetriyl; M is zero; J, K, and L are each equal to one; R³ and R⁴ are each nonylphenyl, R⁵ is benzyl; and c, f, and i are each zero.
 5. An aqueous composition of claim 1, wherein said thickener is a mixture of compounds wherein for each compound J, K, L and M are each equal to one; R³, R⁴, R⁵ and R⁶ are each nonylphenyl, c, f, i, and l, are each zero; and R¹ is ##STR31##
 6. An aqueous composition comprising water and a thickening-effective amount of a thickener of the formula wherein NP is a nonylphenyl group and EO is an ethyleneoxy group.
 7. An aqueous composition comprising water and a thickening-effective amount of a thickener of the formula ##STR32## wherein NP is a nonylphenyl group and EO is an ethyleneoxy group.
 8. A composition of claim 1 further comprising from about 1% to about 30% by weight of a viscosity modifier selected from the group consisting of a liquid polyol, a liquid ethoxylated C₁₋₈ alcohol, a liquid ethoxylated C₁₋₈ carboxylic acid, a liquid propoxylated C₁₋₈ alcohol, a liquid propoxylated C₁₋₈ carboxylic acid.
 9. A composition of claim 8 wherein said liquid polyol is 1,2-propylene glycol.
 10. A composition of claim 8 wherein said liquid ethoxylated C₁₋₈ alcohol is butoxy triglycol.
 11. A composition of claim 8 wherein said liquid ethoxylated C₁₋₈ alcohol is butyl carbitol.
 12. An aqueous composition of claim 8 comprising about 40% by weight of water, about 40% by weight of said thickener and about 20% by weight of butoxy triglycol.
 13. A latex composition comprising water, an emulsion polymer and from about 0.1% to about 10% by weight based emulsion polymer solids of a thickener of the formula ##STR33## wherein R¹ is a member selected from the group consisting of straight chain or branched aliphatic groups having from 3 to about 50 carbon atoms, cycloalkyl groups having from 4 to 20 carbon atoms, straight chain or branched unsaturated aliphatic groups having from 3 to about 40 carbon atoms, cycloalkenyl groups having from 5 to about 20 carbon atoms, and aromatic groups having from 6 to about 21 carbon atoms having a valence of 3 or 4; each of c, f, i, and l is independently 0 or any integer from about 50 to about 200 with the proviso that at least two of c, f, i and l cannot be 0; each of J, K, L and M is 0 or 1, provided that at least three of J, K, L and M are 1; each of R³ -R⁶ is independently an aliphatic or aromatic group having from 1 to 50 carbon atoms; and each AO is independently an ethyleneoxy, 1,2-propyleneoxy, 1,2-butyleneoxy group or combinations thereof and when one of J, K, L or M is 0, the valence is filled by hydrogen.
 14. A composition of claim 13 wherein R¹ is 1,2,3-propanetriyl; M is zero; J, K and L are each equal to one; R³ and R⁴ are each nonylphenyl, R⁵ is benzyl, substituted benzyl, or C₅₋₁₀ alkyl; (AO) is ethyleneoxy, and c, f, and i are each zero.
 15. A composition of claim 13 wherein R¹ is ##STR34## wherein J, K, L and M are each equal to one; R³, R⁴, R⁵ and R⁶ are each nonylphenyl, and c, f, i, and l, are each zero.
 16. An aqueous composition of claim 13 wherein said thickener is a mixture of compounds wherein for each compound R¹ is 1,2,3-propanetriyl; M is zero; J, K, and L are each equal to one; R³ and R⁴ are each nonylphenyl, R⁵ is benzyl; and c, f, and i are each zero.
 17. An aqueous composition of claim 13 wherein said thickener is a mixture of compounds wherein for each compound J, K, L and M are each equal to one; R³, R⁴, R⁵ and R⁶ are each nonylphenyl, c, f, i, and l are each zero; and R¹ is ##STR35##
 18. An aqueous composition comprising water, an emulsion polymer and from about 0.1% to about 10% by weight based on said emulsion polymer solids of a thickener of the formula wherein NP is a nonylphenyl group and EO is an ethyleneoxy group.
 19. An aqueous composition comprising water, an emulsion polymer and from about 0.1% to about 10% by weight based on said emulsion polymer solids of a thickener of the formula ##STR36## wherein NP is a nonylphenyl group and EO is an ethyleneoxy group.
 20. A composition of claim 13 further comprising from about 1% to about 30% by weight of a viscosity modifier selected from the group consisting of a liquid polyol, a liquid ethoxylated C₁₋₈ alcohol, a liquid ethoxylated C₁₋₈ carboxylic acid, a liquid propoxylated C₁₋₈ alcohol, a liquid propoxylated C₁₋₈ carboxylic acid.
 21. A composition of claim 20 wherein said liquid polyol is 1,2-propylene glycol.
 22. A composition of claim 20 wherein said liquid ethoxylated C₁₋₈ alcohol is butoxy triglycol.
 23. A composition of claim 20 wherein said liquid ethoxylated C₁₋₈ alcohol is butyl carbitol.
 24. An aqueous composition of claim 20 comprising about 40% by weight of water, about 40% by weight of said thickener and about 20% by weight of butoxy triglycol.
 25. A latex composition of claim 13 wherein said composition has an ICI viscosity of from about 0.7 to about 3.0 poise and a Stormer viscosity of from about 65 to about 110 KU.
 26. A process for making a compound for of the formula ##STR37## wherein R¹ is a member selected from the group consisting of straight chain or branched aliphatic groups having from 3 to about 50 carbon atoms, cycloalkyl groups having from 4 to 20 carbon atoms, straight chain or branched unsaturated aliphatic groups having from 3 to about 40 carbon atoms, cycloalkenyl groups having from 5 to about 20 carbon atoms, and aromatic groups having from 6 to about 21 carbon atoms having a valence of 3 or 4; each of c, f, i, and l is independently 0 or any integer from about 50 to about 200 with the proviso that at least two of c, f, i and l cannot be 0; each of J, K, L and M is 0 or 1, provided that at least three of J, K, L and M are 1; each of R³ -R⁶ is independently an aliphatic or aromatic group having from 1 to 50 carbon atoms; and each AO is independently an ethyleneoxy, 1,2-propyleneoxy, 1,2-butyleneoxy group or combinations thereof and when one of J, K, L or M is 0, the valence is filled by hydrogen which comprises the steps of:(i) forming an adduct of the formula R¹ --O--(AO)_(c) --OH, wherein R¹, AO and c are defined as above, with the proviso c cannot be 0; (ii) reacting said adduct with a compound of the formula R³⁻⁶ --Y, wherein R³⁻⁶, are defined as above and Y is a functional group capable of reacting with the terminal --OH group of said adduct.
 27. An aqueous composition consisting essentially of:(a) from about 1 to about 50% by weight of a mixture of compounds of Formula V, ##STR38## wherein each of e, h, k and n is equal to 100 or 125, (b) water, and (c) from about 1 to about 30% by weight of a viscosity modifier which is a liquid ethoxylated C₈ alcohol. 